TWI709612B - Composition for forming peeling layer - Google Patents

Abstract

The present invention can maintain the adhesion with the glass substrate provided with the peeling layer without peeling at the interface with the glass substrate. In addition, the layer or layer group formed on the upper part of the peeling layer can be easily peeled off The composition for forming the peeling layer by layer peeling. The present invention provides a composition for forming a peeling layer disposed directly above a glass substrate, wherein the composition has (A) aromatic polyimide and/or aromatic polyimide precursor; and (B) Amine solvent: The aromatic polyimide derived from (A) above satisfies the following (1) to (4).

(1) The temperature at which the weight change is reduced by 1% during heating is above 500°C; (2) At a wavelength of 1000nm, the refractive index is 1.7 or more; (3) At a wavelength of 1000nm, the difference between the refractive index and the birefringence is 0.15 or more ; And (4) The surface energy is 40 dyne/cm or more.

Description

Composition for forming peeling layer

The present invention relates to a composition for forming a peeling layer provided directly above a glass substrate.

In recent years, electronic devices are required to provide performances such as bending functions or thinning and weight reduction. Therefore, it is required to use a lightweight flexible plastic substrate to replace the heavy and fragile glass substrate that cannot be bent. In addition, the new generation of displays requires the development of an active full-color TFT display panel using a lightweight flexible plastic substrate.

Therefore, various methods of manufacturing electronic devices using resin films as substrates are being reviewed, and the process of converting existing TFT devices to manufacturing new-generation displays is being reviewed.

Patent Documents 1, 2 and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate. After the plastic substrate is formed on the thin film layer, a laser is irradiated from the glass surface side, and the hydrogen gas generated by the crystallization of the amorphous silicon , The method of peeling the plastic substrate from the glass substrate.

In addition, Patent Document 4 discloses that the technique disclosed in Patent Documents 1 to 3 is used to bond the peeled layer (described as "transferred layer" in Patent Document 4). Paste on the plastic film to complete the method of liquid crystal display device.

However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, must use a highly transparent substrate to pass the substrate. In addition, in order to release the hydrogen contained in the amorphous silicon, it is necessary to provide sufficient Energy, it is necessary to irradiate a larger laser light, there is a problem of damage to the peeled layer. In addition, the laser processing requires a long time and it is difficult to peel off the peeled layer with a large area. Therefore, it is also difficult to improve the productivity of device manufacturing.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-125929.

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-125931.

[Patent Document 3] WO2005/050754 pamphlet.

[Patent Document 4] Japanese Patent Application Laid-Open No. 10-125930.

Therefore, the object of the present invention is to solve the above-mentioned problems.

Specifically, the object of the present invention is to provide a composition for forming a peeling layer for peeling without causing damage to a substrate suitable for a flexible electronic device.

In addition, the object of the present invention, in addition to the above-mentioned objects, or in addition to the above-mentioned objects, provides that the adhesion between the glass substrate and the glass substrate provided with the peeling layer can be maintained, and the There is no peeling at the interface of the substrate. In addition, the layer or layer group formed on the upper part of the peeling layer can be easily peeled from the peeling layer to form the composition for the peeling layer.

The inventor discovered the following invention.

<1> A composition, which is a composition for forming a peeling layer disposed directly above a glass substrate, wherein the composition has (A) an aromatic polyimide and/or an aromatic polyimide precursor; And (B) an amide-based solvent; the aromatic polyimide derived from (A) above satisfies the following (1) to (4).

(1) The temperature at which the weight change is reduced by 1% during heating is above 500°C; (2) At a wavelength of 1000nm, the refractive index is 1.7 or more; (3) At a wavelength of 1000nm, the difference between the refractive index and the birefringence is 0.15 or more ; And (4) The surface energy is 40 dyne/cm or more.

<2> In the above-mentioned <1>, the component (A) can be produced using at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine.

<3> In the above <2>, the amount of p-phenylenediamine and/or terphenyldiamine can be 70 mol% or more in 100 mol% of the total diamine component.

<4> In any of the above <1>~<3>, the component (A) can be an aromatic having a first skeleton selected from the group consisting of biphenyl skeleton, imidazole skeleton and oxazole skeleton Produced by diamine.

<5> In any of the above <1>~<4>, the component (A) can be an acid dianhydride having a second skeleton selected from the group consisting of benzene skeleton, naphthalene skeleton and biphenyl skeleton Produced by.

<6> In any of the above <1>~<3>, (B) component may be a solvent represented by the following formula (I), and/or (II) (where R ¹ and R ² are each independently represented A solvent represented by an alkyl group having 1 to 4 carbon atoms, and h represents a natural number.

<7> A peeling layer which is formed using any one of the above-mentioned <1> to <6> composition and is provided directly above the glass substrate.

<8> A method of manufacturing a peeled body, which is a method of obtaining a peeled body by having the following steps: a) coating the composition described in any one of <1> to <6> above on a glass substrate Then, a step of forming a peeling layer; b) a step of forming a peeled body on the peeling layer; and c) a step of peeling the peeled body at the interface between the peeling layer and the peeled body.

The above-mentioned problems can be solved by the present invention.

Specifically, the present invention can provide a peeling layer that can be peeled off without causing damage to substrates suitable for flexible electronic devices, etc. Used composition.

Furthermore, according to the present invention, in addition to the above-mentioned objects or the above-mentioned objects, it is provided that the adhesion to the glass substrate provided with the peeling layer can be maintained without peeling at the interface with the glass substrate. In addition, it is formed on the peeling layer The upper layer or layer group can be easily peeled from the peeling layer to form the composition for the peeling layer.

[The form of implementing the invention]

The present application provides a composition for forming a peeling layer that is arranged directly above a glass substrate.

The composition is described in detail below.

<Composition>

The composition of the present invention has (A) an aromatic polyimine and/or an aromatic polyimine precursor; and (B) an amide-based solvent.

<<(A) Ingredient>>

(A) The component is an aromatic polyimide and/or an aromatic polyimide precursor.

Here, "aromatic polyimine" refers to the diamine component and the acid dianhydride component constituting the polyimine, both of which have aromatic groups. Therefore, the polyimide obtained by it is mainly The main chain has an aromatic group.

In addition, "aromatic polyimide precursor" refers to the above-mentioned aromatic polyimide precursor, and typically includes, for example, polyamide and polyamide Esters and polyisoimines are preferably polyamides.

Specifically, the aromatic polyimine can be divided into a diamine component and an acid dianhydride component constituting the polyimine, and the following may be mentioned, but it is not limited thereto.

<Diamine component>

The diamine component having an aromatic group includes, for example, 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diamine Benzene (o-phenylenediamine), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine , 2,5-Dimethyl-p-phenylenediamine 2, 6-Dimethyl-p-phenylenediamine 2,4-bis(amino-t-butyl)toluene 2,4,6-trimethyl Phenyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene- 1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis(trifluoromethyl)benzene-1,2-diamine, etc. , 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4 ,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ',5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl) sulfide, 4,4'-diaminobenzaniline, 3 ,3'-Dichlorobenzidine, 3,3'-Dimethylbenzidine, 2,2'-Dimethylbenzidine, 3,3'-Dimethoxybenzidine, 2,2'-Dimethyl Oxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-di Amino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4,4'-diamino di Phenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-di Aminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-amino Phenyl) propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfene, 3,4'-di Amino diphenyl sulfene, 4,4'-diamino diphenyl sulfene, 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3' -Bis(trifluoromethyl)biphenyl-4,4'-diamine, 3,3',5,5'-tetrafluorobiphenyl-4,4'-diamine, 4,4'-diamine Diamines of two benzene nuclei such as aminooctafluorobiphenyl, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4- Bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3 '-Diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-bis(4-phenylphenoxy)benzophenone , 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide) Benzene, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[ 2-(4-aminophenyl)isopropyl)benzene and other benzene nuclei of 3 diamines, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis( 4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[ 3-(3-Aminophenoxy)phenyl]ether, bis[3-(4-amine Phenyloxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3- (3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, Bis[4-(4-aminophenoxy)phenyl]one (bis(4-aminophenoxy)benzophenone), bis[3-(3-aminophenoxy)phenyl] Thioether, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-amino) Phenoxy) phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy) phenyl] sulfide, bis[4- (3-aminophenoxy) phenyl] ash, bis[4-(4-aminophenoxy) phenyl] ash, bis[3-(3-aminophenoxy) phenyl] methane, Bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)benzene Yl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2, 2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3- (3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]- 1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 9,9-bis(4-amino) Phenyl) pyrene, 9,9-bis(4-aminophenyl) pyrene, 9,9'-bis(4-aminophenoxyphenyl) pyrene, etc. Diamines with more than 4 benzene nuclei, 5 -Amino-2-(p-aminophenyl)benzoxazole, 5-amino-2-(m-aminophenyl)benzoxazole, 6-amino-2-(p-amine Phenyl)benzoxazole, 6-amino-2-(m-aminophenyl)benzoxazole, 2,2'-p-phenylene bis(5-aminobenzoxazole) , 2,2'-p-phenylene bis(6-aminobenzoxazole), 1-(5-aminobenzoxazolo)-4-(6-aminobenzoxazole) )Benzene, 2,6- (4,4'-diaminodiphenyl) benzo[1,2-d:5,4-d'] dioxazole (benzobisoxazole), 2,6-(4,4'-diaminodiphenyl) Phenyl)benzo[1,2-d:4,5-d']dioxazole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:5 ,4-d']dioxazole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:4,5-d']dioxazole, 2,6 -(3,3'-diaminodiphenyl)benzo[1,2-d:5,4-d']dioxazole, 2,6-(3,3'-diaminodiphenyl) ) Benzo[1,2-d:4,5-d']dioxazole, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, etc. Diamines of benzoxazole structure, etc., but are not limited thereto. These can be used alone or in combination of two or more kinds.

As for the diamine component, at least one diamine component selected from the group consisting of p-phenylenediamine and terphenyldiamine can be used in a certain aspect.

In this case, the amount of p-phenylenediamine and/or terphenyldiamine can be 70 mol% or more in 100 mol% of the total diamine component, preferably 80 mol% or more, and more preferably More than 90 mol%.

In other respects, the diamine component may be an aromatic diamine having a first skeleton of at least one selected from the group consisting of a biphenyl skeleton, an imidazole skeleton, and an oxazole skeleton.

<Acid dianhydride component>

Examples of the acid dianhydride component having an aromatic group include acid dianhydride having a benzene skeleton, acid dianhydride having a naphthalene skeleton, and acid dianhydride having a biphenyl skeleton, but are not limited thereto.

Specifically, for example, trimellitic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Anhydride, 2,3,3',4'- Biphenyl tetracarboxylic dianhydride, oxygen diphthalic anhydride, diphenyl sulfide-3,4,3',4'-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) sulfide Two anhydrates, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane two anhydrates, 2,3,3',4'-two Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane two anhydride, 2,2-bis (3,4-Dicarboxyphenyl) propane two anhydrate, p-phenylene bis (pyromellitic acid monoester anhydride), p-methyl phenylene bis (pyromellitic acid monoester anhydride), p -(2,3-Dimethylphenylene) bis (pyromellitic acid monoester anhydride), 4,4'-biphenylene bis (pyromellitic acid monoester anhydride), 1,4-naphthalene bis (Pyromellitic acid monoester anhydride), 2,6-naphthalene bis(pyromellitic acid monoester anhydride) 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4 ,4'-tetracarboxylic dianhydride, m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic Acid dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene anhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene anhydride, 1,4- Bis(3,4-dicarboxyphenoxy)biphenyl dianhydrate, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydrate, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropylene) diphthalic dianhydride, N, N'-(2,2'-bis{trifluoromethyl}-[1,1'-biphenyl]-4,4'-diyl)bis(1,3-dioxo-1,3- Dihydroxybenzofuran-5-carboxyamide), etc., but not limited thereto. These can be used alone or in combination of two or more kinds.

<The characteristics of aromatic polyimide from (A)>

The composition of this case, the aromatic polyimide from (A), has the following characteristics (1) to (4).

<<(1)~(4) Features>>

(1) The temperature at which the weight change during heating reduces by 1% is 500°C or higher, preferably 520°C or higher, more preferably 550°C or higher; (2) At a wavelength of 1000 nm, the refractive index is 1.7 or higher; (3) At a wavelength of 1000 nm, the difference between the refractive index and the birefringence is 0.15 or more, preferably 0.16 or more; and (4) The surface energy is 40 dyne/cm or more, preferably 45 to 70 dyne/cm, more preferably 45 to 60 dyne/cm .

Also, "aromatic polyimide derived from (A)" or "aromatic polyimide derived from (A)" refers to the case where the component (A) is composed of only "aromatic polyimide" , Refers to the "aromatic polyimide". In addition, when component (A) is composed only of "aromatic polyimide precursor", it means the "aromatic polyimide" when all the precursors become "aromatic polyimide" . (A) When the component has "aromatic polyimide A" and "aromatic polyimide precursor B", it means "aromatic polyimide precursor B" formed by "aromatic polyimide precursor B" The whole of "Imidine B'" and "Aromatic polyimide A".

By having these characteristics, when the peeling layer is formed from the composition, the adhesion between the peeling layer and the glass substrate becomes good, and when the peeled body is formed on the peeling layer, the peeled body can be It is easy to peel off by cutting in with a cutting knife.

<(B) Ingredient>

The desired composition has an amide solvent as the component (B).

The amide-based solvent refers to a liquid having an amide group and an alkyl amide group.

Examples of the amide-based solvent include N-methylpyrrolidone, N-ethylpyrrolidone, DMAc, DMF, Equamide M, and Equamide B (manufactured by Idemitsu Kosan Co., Ltd.), but are not limited thereto.

The amide-based solvent may be a solvent represented by the following formula (I), and/or (II) (wherein R ¹ and R ² each independently represent an alkyl group with 1 to 4 carbon atoms, and h represents a natural number). Of solvents.

In addition to the above-mentioned (A) component and (B) component, the composition of this case may have various components. For example, a crosslinking agent (hereinafter also referred to as a crosslinking compound) can be mentioned, but it is not limited thereto.

The crosslinkable compound includes, for example, a compound containing two or more epoxy groups, a melamine derivative in which the hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both of them, and benzoguanamine Derivatives, glycolurils, etc., but are not limited thereto.

Specific examples of crosslinkable compounds can be given below, but are not limited to these.

Compounds containing two or more epoxy groups, for example, Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, Celloxide 3000 (above are (Stock) Daicel) and other epoxy compounds having a cyclohexene structure; Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (The above are made by Japan Epoxy Resin (Stock) (Currently: Mitsubishi Chemical Corporation, jER (registered trademark) series), etc. Bisphenol A epoxy compound; Epikote 807 (Japan Epoxy Resin (Japan Epoxy Resin)), etc. Bisphenol F epoxy compound; Epikote 152. Epikote 154 (above are manufactured by Japan Epoxy Resin (stock) (currently: manufactured by Mitsubishi Chemical Co., Ltd., jER (registered trademark) series)), EPPN201, EPPN202 (above are manufactured by Nippon Kayaku Co., Ltd.), etc. Varnish-type epoxy compounds; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (the above are manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Resin (stock) (Currently: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series), etc. novolac epoxy compounds; V8000-C7 (made by DIC Corporation), etc. naphthalene epoxy compounds; Denacol EX-252 (NagaseChemtex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above manufactured by BASF), Epiclon 200, Epiclon 400 (above are DIC (stock)) , Epikote 871, Epikote 872 (the above are made by Japan Epoxy Resin (stock) (currently: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series)), ED-5661, ED-5662 (the above are Celanese coating (shares) Made) and other alicyclic epoxy compounds; Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421 , Denacol EX-313, Denacol EX- 314. Aliphatic polyglycidyl ether compounds such as Denacol EX-312 (manufactured by NagaseChemtex (stock)), etc.

Melamine derivatives, benzoguanamine derivatives, or glycolurils in which the hydrogen atom of an amino group is substituted by methylol, alkoxymethyl, or both of them, for example, in one triazine ring, MX-750 substituted with an average of 3.7 base methyl groups, MW-30 substituted with an average of 5.8 methoxymethyl groups in one triazine ring (the above are manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301 , Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc. Methoxy methylated melamine; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel Methoxy methylated butoxy methylated melamine such as 254; butoxy methylated melamine such as Cymel 506 and Cymel 508; such as Cymel 1141 methoxy methylated isobutoxy methyl containing carboxyl group Alkylated melamine; such as Cymel 1123 methoxymethylated ethoxymethylated benzoguanamine; such as Cymel 1123-10 methoxymethylated butoxymethylated benzoguanamine; such as Cymel 1128 Butoxymethylated benzoguanamine; such as Cymel 1125-80 containing carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine; such as Cymel 1170 butoxymethylated glycoluril; such as Cymel 1172 Hydroxymethylated glycoluril (above is manufactured by Mitsui Cyanamid (stock) (currently: Cytec Industries (stock) in Japan)).

With the composition of this case, a peeling layer can be formed directly above the glass substrate.

For example, on a glass substrate, the composition of this case is coated by a conventionally known method, and the resulting coating film is heated at a specific temperature to form Peeling layer.

In addition, the peeled body layer may be formed on the peeling layer. The peeled-off body layer may be one layer or multiple layers. When making various installations, there are actually multiple layers.

Among the to-be-peeled body layers, the layer directly above the peeling layer depends on the peeling layer used, but it is possible to use those that have better peelability with the peeling layer, in other words, those with poor adhesion to the peeling layer used.

The other aspect of this case is to provide a method of manufacturing the peeled body.

In this method, a peeled body can be obtained by having the following steps.

a) the step of forming a peeling layer after coating the composition of the present case on the glass substrate; b) the step of forming a peeled body on the peeling layer; and c) the interface between the peeling layer and the peeled body will be The step of peeling the peeled body; in step b), the "peeled body" may be one layer or multiple layers.

In addition, in the "peeled body", the layer directly above the peeling layer depends on the peeling layer used, but the peeling layer can be used with better peelability, in other words, the adhesiveness of the peeling layer is different from that of the peeling layer used. The best.

The present invention will be described below based on examples, but the present invention is not limited to these examples.

[Example]

The abbreviations used in this embodiment are listed and described below.

<Solvent>

NMP: N-methylpyrrolidone.

<Amines>

PDA: p-phenylenediamine.

APAB: 2-(3-aminophenyl)-5-aminobenzimidazole.

DATP: 4,4"-diamino-p-terphenyl.

6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

<acid dianhydride>

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

BA-TME: 4,4'-Biphenylene bis(pyromellitic acid monoester anhydride).

PMDA: trimellitic dianhydride.

<aldehyde>

IPHA: isophthalaldehyde.

[Measurement of number average molecular weight and weight average molecular weight]

The weight-average molecular weight (hereinafter referred to as "Mw") and molecular weight distribution of the polymer are determined by using GPC equipment (Shodex (registered trademark) columns KF803L and KF805L) from Japan Seiko Co., Ltd. as the dissolution solvent of dimethylformaldehyde Amide was measured under the conditions of a flow rate of 1 ml/min and a column temperature of 50°C. In addition, Mw is a polystyrene conversion value.

<Synthesis example> <Synthesis Example 1 Synthesis of Polyimide Precursor P1>

Dissolve PDA 17.8g (0.164 mol), DATP 2.38g (0.009 mol) and APAB 2.05g (0.009 mol) in NMP 425g, and add 52.8g (0.179 mol) of BPDA, then add NMP 7.4g again , In a nitrogen environment, react at 23°C for 24 hours. The obtained polyimide precursor P1 has a Mw of 63,000 and a molecular weight distribution of 9.9.

<Synthesis Example 2 Synthesis of Polyimide Precursor P2>

After dissolving 30.8 g (0.118 mol) of DATP in 425 g of NMP and adding 34.1 g (0.116 mol) of BPDA at the same time, 10 g of NMP was added again, and the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P2 had an Mw of 70,700 and a molecular weight distribution of 9.7.

<Synthesis Example 3 Synthesis of Polyimide Precursor P3>

Dissolve PDA 20.261g (0.1875 mol) and TPDA 12.206g (0.0469 mol) in NMP 617.4g, after cooling to 15°C, add PMDA 50.112g (0.2298 mol), and react at 50°C under nitrogen atmosphere 48 hours. The obtained polyimide precursor P3 had an Mw of 82,100 and a molecular weight distribution of 2.7.

<Synthesis Example 4 Synthesis of Polyimide Precursor P4>

9.66 g (0.089 mol) of PDA and 1.05 g (0.005 mol) of APAB were dissolved in 440 g of NMP, 49.2 g (0.092 mol) of BP-TME was added, and the reaction was carried out at room temperature for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P4 had a Mw of 57,000 and a molecular weight distribution of 9.3.

<Synthesis Example 5: Synthesis of Polyimide Precursor P5>

After dissolving 3.176 g (0.02937 mol) of PDA in 88.2 g of NMP, and adding 8.624 g (0.02931 mol) of BPDA, the reaction was carried out at 23°C for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P5 had a Mw of 107,300 and a molecular weight distribution of 4.6.

<Synthesis Example 6 Synthesis of polybenzoxazole precursor (P6)>

After dissolving 3.18 g (0.059 mol) of 6FAP in 70 g of NMP and adding 7.92 g (0.060 mol) of IPHA, the reaction was carried out at 23°C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 107,300 and the molecular weight distribution was 4.6.

<Synthesis Example 7: Synthesis of Polyimide Precursor P7> PMDA(98)//p-PDA(100)

10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. 19.922 g (91 mmol) of PMDA was added to the resulting solution, and reacted at 23°C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 55,900 and the molecular weight distribution was 3.1.

<Production of peeling layer substrate>

Dilute the P1~P7 obtained in the above synthesis examples 1~7 with NMP to 4wt%, and use a spin coater to coat them on a 100mm×100mm glass substrate (OA-10G alkali-free glass) or silicon wafer. Firing in an oven under hardening conditions A to C to produce a peeling layer.

Curing condition A: 120°C, hold for 30 minutes→heat up→300°C, hold for 60 minutes→heat up→400°C, hold for 60 minutes. In addition, the temperature increase rate is 10°C/min.

Curing condition B: 120°C, hold for 30 minutes→heat up→180°C, hold for 20 minutes→heat up→240°C, hold for 20 minutes→heat up→300°C, hold for 20 minutes→heat up→400°C, hold for 20 minutes Minutes→heating→450℃,maintain for 60 minutes. In addition, the temperature increase rate is 10°C/min.

Curing condition C: Hold at 80°C for 10 minutes → increase temperature → 300°C for 30 minutes → increase temperature → 400°C for 30 minutes. In addition, the temperature increase rate is 10°C/min.

The film thickness of the obtained coating film was measured using a contact type film thickness measuring device (Dektak 3ST manufactured by ULVAC Co., Ltd.).

Table 1 shows the used P1~P7 precursors, coated substrates, curing conditions, and the thickness of the release layer produced.

<Cross-cut test I>

For the substrates with the peeling layer of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the checkered test I was used to confirm the adhesion of the substrate (glass or silicon wafer)/peeling layer.

The checkered test I was carried out as follows.

(1) Make 100 squares of 1 mm square on the peeling layer.

(2) Then, stick to the above square with an adhesive tape (Salu Tie tape (registered trademark)), and then perform the peeling step.

(3) After the peeling step, calculate the squares remaining on the substrate.

<The index of the results of the grid test I>

The results of the checkered test and the degree of peeling are indicated by the following indicators.

5B: No peeling.

4B: Peeling less than 5%.

3B: 5~15% peeling.

2B: 15~35% peeling.

1B: 35~65% peeling.

0B: 65%~80% peeling.

B: 80%-95% peeling.

A: 95% to less than 100% peeling.

AA: 100% peeling.

Different from the above-mentioned checkered test I, for the substrates with peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the characteristics of the components constituting the peeling layer were measured, that is, (1) shows heating The temperature at which the weight change reduces by 1% by weight, (2) the refractive index at a wavelength of 1000 nm, (3) the birefringence at a wavelength of 1000 nm, and (4) the surface energy. In addition, the measurement conditions for each characteristic are as follows.

<(1) Display the temperature at which the weight change during heating reduces by 1%>

TD-DTA2000ST manufactured by Bruker (stock) was used to perform thermogravimetric (TG) measurement in a nitrogen environment to find the temperature at which the weight was reduced by 1%.

<(2) Refractive index and (3) Birefringence at wavelength 1000nm>

A high-speed spectroscopic ellipsometer M-2000 (manufactured by J.A. Woollam Japan (stock)) was used to measure the refractive index and birefringence. In addition, the refractive index is the in-plane refractive index at a value of 1000 nm, and the birefringence is the difference between the in-plane refractive index and the out-of-plane refractive index.

<(4) Surface Energy>

Use the automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) to measure the peeling of P1~P7 obtained in the above synthesis examples 1~7 The surface energy of the layer. In addition, the solvent used in the measurement is water and methylene iodide, and the contact angle of these solvents is calculated.

<Formation of the peeled body and its peeling test (square test II)>

The peeled body was formed on the substrate provided with the peeling layer of Examples 1 to 5 and Comparative Examples 1 to 3, and the degree of peeling was confirmed by the checker test II.

<<Production of peeled body layer>>

A polyimide layer as a peeled body is formed on the peeling layer of the substrate provided with the peeling layer.

Specifically, as shown in Table 1, on the release layer of the substrate provided with the release layer of Examples 1 to 5 and Comparative Examples 1 to 3, the precursor obtained in Synthesis Example 5 or Synthesis Example 1 was coated with a coating bar.物P5 or P1. Then, keep the oven at 120°C for 30 minutes→heat up→180°C for 20 minutes→heat up→240°C/maintain for 20 minutes→heat up→300°C for 20 minutes→heat up→400°C for 20 minutes Minutes→heating→450°C for 60 minutes (both the temperature rise rate is 10°C/min) for curing to produce a peeled body layer made of polyimide with a film thickness of 15μm.

<<Checkered Test II>>

With respect to the substrate provided with the peeled body layer and the peeled layer obtained above, the adhesion between the peeled body layer and the peeled layer was confirmed by the checker test II.

The grid test II is the same as the grid test I.

Table 2 shows (1) shows that the weight change during heating is reduced by 1% by weight Temperature (in Table 2, "indicated by (1)"), (2) Refractive index at a wavelength of 1000nm (indicated by "(2)" in Table 2), (3) Refractive index and birefringence of (2) The difference (in Table 2, "indicated by (3)"), (4) Surface energy (indicated by "(4)" in Table 2, but the unit is dyne/cm), and the polyamide used in the peeled body layer Amine precursor, and the results of grid tests I and II.

Table 2 shows the following situation. The result of Test I of the peeling layer of Examples 1 to 5 was 5B, so it was found that the peeling layer was not peeled from the substrate, and the result of Test II was AA, so it was found that only the peeled body layer was peeled from the peeling layer. In other words, it was found that the peeling layer formed from the composition for the peeling layer of the present invention produced the desired peeling result.

In addition, the results of Test I of Comparative Example 1 and Comparative Example 3 were AA, and therefore, it was found that the peeling layer was peelable from the substrate. In other words, it is understood that Comparative Example 1 and Comparative Example 3 cannot obtain the desired peeling result. In addition, both Test I and Test II of Comparative Example 2 are 5B, so it is found that even at the interface between the peeling layer and the substrate, or the interface between the peeling layer and the peeled body layer, the peeling does not occur, and the desired peeling result cannot be obtained. .

Claims (4)

A composition, which is a composition for forming a peeling layer directly above a glass substrate, wherein the composition has (A) an aromatic polyimide and/or an aromatic polyimide precursor; and (B ) Amide-based solvent; the aromatic polyimide from the aforementioned (A), which satisfies the following (1) to (4), (1) the temperature at which the weight change during heating reduces by 1% is above 500°C; (2) At a wavelength of 1000 nm, the refractive index is 1.7 or more; (3) At a wavelength of 1000 nm, the difference between the refractive index and the birefringence is 0.15 or more; and (4) The surface energy is 40 dyne/cm or more, and the aforementioned component (A) is used At least one diamine component selected from the group consisting of p-phenylenediamine and terphenyl diamine, wherein the amount of p-phenylenediamine and/or terphenyl diamine is 100 moles of total diamine component In %, it is 90 mol% or more. The composition of the first item of the scope of patent application, wherein the aforementioned component (A) is manufactured using an aromatic diamine having a first skeleton of at least one selected from the group consisting of biphenyl skeleton, imidazole skeleton and oxazole skeleton . The composition of the first item of the scope of the patent application, wherein the aforementioned component (A) is manufactured using an acid dianhydride having a second skeleton selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton. For example, the composition of any one of items 1 to 3 in the scope of patent application, wherein the aforementioned component (B) is a solvent represented by the following formula (I), and/or (II) (where R ¹ and R ² are each Independently represents an alkyl group with 1 to 4 carbon atoms, h represents a natural number) represents the solvent,